N-aryl-substituted dialkanolamino polyurethanes

ABSTRACT

Molding compositions may be prepared from a solution of an unsaturated polyester prepared from an ethylenically unsaturated dicarboxylic acid and diol, in a copolymerizable monomer exemplified by styrene, vinyl toluene and alkyl acrylates. The solution also contains 0.1 to 5.0 percent weight of an N-arylsubstituted diaklanolamino polyurethane prepared from the reaction product of an N-aryl substituted dialkanolamine, a diisocyanate, and one of a monoisocyanate, a monothioalcohol, or monoamine.

United States Patent Eimers [4 1 Oct. 10, 1972 I54] N-ARYL-SUBSTITUTED DIALKANOLAMINO POLYURETHANES [72] Inventor: Erich Eimers, Krefeld, Germany [22] Filed: Sept. 25,1970

[21] Appl. No.: 75,715

Related US. Application Data [62] Division of Ser. No. 735,51 1, June 10, 1968,

abandoned.

[30] Foreign Application Priority Data July 4, 1967 Germany ..F 52853 [52] US. Cl. ..260/859 R, 260/75 NH, 260/75 TN, 260/77.5 AA, 260/77.5 AM, 260/77.5 AP, 260/77.5 MA

[51] Int. Cl. ..C08g 41/04 [58] Field of Search ..260/859, 77.5 AP, 77.5 AA

[56] References Cited UNITED STATES PATENTS 3,061,470 10/1962 Kuemmerer ..l l7/l38.8

3,l43,5 I7 8/1964 Heiss ..260/l8 FOREIGN PATENTS OR APPLICATIONS 994,297 6/1965 Great Britain ..260/859 OTHER PUBLICATIONS Flory- Principles of Polymer Chemistry, Cornell University, Ithaca, NY. (1953) pages 40- 41, 45- 46 QD 281 P6F66 Lenz Organic Chemistry of Synthetic High Polymers, Interscience, New York, (1967) pages 3, 4, l1, 1 53-56, 186- 189. OD 281 P6L4 Primary Examiner-Paul Lieberman I Attorney-Connolly and Hutz 6 ABSTRACT Molding compositions may be prepared from a solution of an unsaturated polyester prepared from an ethylenically unsaturated dicarboxylic acid and diol, in a copolymerizable monomer exemplified by styrene, vinyl toluene and alkyl acrylates. The solution also contains 0.1 to 5.0 percent weight of an N-aryl-substituted diaklanolamino polyurethane prepared from the reaction product of an N-aryl substituted dialkanolamine, a diisocyanate, and one of a monoisocyanate, a monothioalcohol, or monoamine.

5 Claims, N0 Drawings 1 2 N-ARYL-SUBSTITUTED DIALKANOLAMINO in the molar ratio of 2: 1 :2 to about 1 1:l0:2, preferably, POLYURETHANES to about 6:5:2, or 1:2:2 to about 10:1 1:2, preferably to CROSS REFERENCE To RELATED APPLICATION about 5 :6:2, at temperatures of about 50 to about 150 C, preferably about 80 to about 120 C, in the This application is a division of application Ser. No. 5 p e e e 0 absence Of So vents. 735,51 1 filed June 10, 1968 and now abandoned. A preferred method of carrying out the process con- The object of the invention comprises N-aryl-sub- Sists in reacting the dialkanolamine and the diisostituted dialkanolamino-polyurethanes containing alkyl cyanate in a molar ratio of 2:1 to about 1 1:1, preferably or aryl terminal groups and corresponding to the to about 6:5, or of 1:2 to about 10:1, preferably to general formula about 5:6, and to reactthe monourethane or monoal- 0 FR; Ar R2 0 0 I Rr-NH-8- H-OH2I IOHz(kH-O- -NH-R-NH-li-O L 0 R2 Al. R2 fl in which Ar denotes aryl, R is alkylene or arylene, R is cohol or monothioalcohol or amine in the stated molar alkyl or aryl, R is H or CH;,, R is O--R or ratio on the reaction product.

Suitable dialkanolamines of the said type are, for example, N-di(P-hydroxyethyl)- or -(p-hydroxypropyl)- aniline, -p-chloroaniline, -pentachloroaniline, -pl or -N toluidine, -diphenylamine and -p-naphthylamine. M v e, Examples of suitable diisocyanates are tetramethylene and hexamethylene diisocyanate, pphenylene diisocyanate, toluylene diisocyanate p,p- R is alkyl, preferably diphenylene diisocyanate, and 1,3,5-triisopropyl-phenylene diisocyanate2,6.

Monoisocyanates which can be used are, for exam- Rz ple, ethyl, propyl, butyl, allyl and methoxymethyl iso- -6H0HzN-Rl cyanate, phenyl isocyanate, pentachlorophenyl iso- 40 cyanate and naphthyl isocyanate.

Suitable monoalcohols and thioalcohols are, for ex- 5 is H alkyl of y 6 is alkyl of aryl, is 1 t0 about ample, ethanol, propanol, butanol and isobutanol and 10, preferably 1 to about 5, the corresponding thioalcohols as well as B-hydroxa process for their production and for their use as addiypropyl methacrylate, but preferably N-methyland N- tives to intermediates of polyester moulding materials. h LNph d h l d N-p-h d At room temperature, the dialkanolamino-polyul ili d -t l idi rethanes are crystallized or highly viscous to solid Suitable primary amines are, for example,

resinous materialsethylamine, n-butylamine, cyclohexylamine, aniline,

The process for their production consists in that a N- l idi h h l i d a h h h i aryl-substituted dialkanolamine 0f the formula Examples of suitable secondary amines are diethyL,

dipropy1-, dibutyl-, diamyl-, diphenyl-, di-p-toluyl-and di-B-naphthylamine as well as mixed amines, such as R2 R2 methylethyl-, ethylpropyl-, ethylbutyl-, ethylphenyl-, 110-116-1120 N-OHz-6H-OH ethyl-p-toluyland ethylnaphthyl-amine, morpholine and piperidine.

Examples of solvents which may be concurrently is reacted with a diisocyanate of the formula used for the preparation of the polyurethanes are dioxan, ethyl acetate, butyl acetate, toluene, o,m,p-xylene and dibutyl ether. These solvents are distilled off when the reaction is completed. However, those solvents are preferred which contain polymerizable vinyl groups, as these not be removed; of with a monoalcohOl, a monothloalcohol Pmna'y they can be added together with the polyurethanes'disand a monoisocyanate of the formula or Secondary amine of the formula solved in them to the moulding material intermediates,

' since they are copolymerized in the course of the sub- H O 4, HS 4 or sequent hardening of the intermediates with the R, hardening products. Solvents of this type are, for example, vinyl acetate, allyl acetate, phthalic acid diallyl ester, 1,l,l-trimethylol-propane triallyl ether, ethyl acrylate, methyl methacrylate, styrene and vinyltoluene.

The preparation of the new polyurethanes may be illustrated by the following Examples 1 to 3,

EXAMPLE 1 (molar ratio 2:1 :2)

195 Parts by weight N-di-(B-hydroxyethyD-ptoluidine (1 mole) are melted in a stirring vessel with the exclusion of moisture and heated to 110 C. 84 Parts by weight hexamethylene diisocyanate (0.5 mole) are then added in the course of 1 hour. The reaction mixture is stirred at the same temperature for a further hour. 1 Parts by weight phenyl isocyanate (1 mole) are then added at 110- 120 C in the course of a further 1% hours. After further stirring at l C for 1 hour, 0.5 parts by weight hydroquinone are added. A yellow-colored resin is obtained.

EXAMPLE 2 (molar ratio 3:222)

292.5 Parts by weight N-di-(p-hydroxyethyl)-ptoluidine (1.5 mole), 168 parts by weight hexamethylene diisocyanate (lmole) and 110 parts by weight phenyl isocyanate (1 mole) are reacted as described in Example 1. The resinous polyurethane is stabilized by the addition of 0.82 parts by weight hydroquinone.

EXAMPLE 3 (molar ratio 3:4:2)

260 Parts by weight N-di-(p-hydroxyethyl)-ptoluidine (1.33 mole) are reacted, as described in Example with 299 parts by weight hexamethylen'e diisocyanate (1.78 mole). 135 Parts by weight N-methyl-N- (p-hydroxyethyl)-aniline are then added at 120 C in the course of 1$ hour. After further stirring at 120 C for 1 hour, the resinous polyurethane is stabilized by the addition of 0.875 parts by weight hydroquinone.

The new polyurethanes are particularly suitable as additives to intermediates of polyester moulding materials, i.e. to solutions of unsaturated polyesters in copolymerizable monomers which are converted, after the further addition of an organic peroxide, mainly a diacyl peroxide, into cold-hardening moulding materials. Added amounts of the polyurethanes of about 0.1

g to aboutS percent by weight, referred to the intermediate of the polyester moulding material will be sufficientfor the said purpose.

The new polyurethanes are characterized by their good compatibility with these intermediates, and the intermediates containing such an additive are themselves characterized by their good stability in storage. It is particularly noteworthy that the reactivity of the moulding materials does virtually not decrease, even if the peroxide is added to the intermediates containing such a polyurethane after prolonged storage.

The unsaturated polyesters comprise, as t is usual, condensation products of a, B-unsaturated dicarboxylic acids, optionally in admixture with other customary dicarboxylic acids, and dialcohols; the copolymerizable monomers also comprise the usual compounds, such as styrene and its homologues, e.g. vinyl-toluene and pchlorostyrene, acrylic and methacrylic acid esters and esters of unsaturated alcohols, e.g. diallyl phthalate.

Diacyl peroxides are, for example, benzoyl, pchlorobenzoyl, benzoylacetyl, phthalyl and lauroyl peroxides. I

The polyurethanes can be added to the moulding material intermediates as such, but preferably dissolved in a copolymerizable monomer, e.g. styrene, in the stated amounts.

The following Examples 4 to 6 illustrate the use of the new polyurethanes as additives to intermediates of polyester moulding materials.

EXAMPLE 4 2.7 Parts by weight of a percent by weight solution of the polyurethane prepared according to Example 1, in styrene, are admixed'with parts by weight of a 70 percent by weight solution of a polyester, 1

prepared from 3,210 parts by weight maleic acid anhydride, 5,421 parts by weight phthalic acid anhydride and 5,616 parts by weight 1,2-propy1ene glycol, in styrene. After the addition of 3 percent by weight of the commercial benzoyl peroxide paste, the polyester moulding mass so produced hardens at 20 C in 7 minutes and 50 seconds. If, however, the intermediate containing the polyurethane is stored at room tempe rature for 3 weeks, the hardening time is almost unchanged: it amounts to 9 minutes and 10 seconds.

EXAMPLE 5 To 3 parts by weight of a 70 percent by weight solution of the polyurethane prepared according to Example 2, in styrene, there are added 100 parts by weight of the solution of polyester in styrene described in Example 4. When the peroxide paste is added immediately after preparation of the solution, the hardening time at 20 C again amounts to 7 minutes and 50 seconds. If the polyurethane-containin g intermediate is first stored for 3 weeks, the hardening time amounts to 8 minutes and 25 seconds.

EXAMPLE 6 To 2.5 parts by weight of a 70 percent by weight solution of the polyurethane preparedaccording to Example 3, in styrene, there are added 100 parts by weight of the polyester solution in styrene described in Example 4. When the peroxide paste is added immediately after the preparation of the solution, the hardening time amounts to 10 minutes and 25 seconds; if the polyurethane-containing intermediate is first stored for 3 weeks, it amounts to 9 minutes and 50 seconds.

What is claimed is:

1. A solution of an unsaturated polyester of an 01,}?- unsaturated dicarboxylic acid and a diol in a liquid copolymerizable monomer containing 0.1 to about 5 percent by weight of a compound produced by the process of reacting a. an N-aryl-substituted dialkanolamine of the formula wherein R is alkylene or arylene and c. a monoisocyanate of the formula wherein R is alkyl, allyl, methoxymethyl or aryl, R is alkyl or wherein Ar, R and R are as aforesaid, R is H, alkyl or aryl and R is alkyl or aryl, the molar ratio of (a):(b):(c) being n:(n+l):2 or (n+l):n:2 wherein the value of n is from 1 to about 10, at a temperature from about 50 to about C.

2. The solution of claim 1 wherein copolymerizable monomer is styrene.

3. The solution of claim 1 wherein Ar is phenyl, monochlorophenyl, pentachlorophenyl, toluyl, diphenyl or naphthyl; R is alkylene having up to six carbon atoms, phenylene, 'toluylene, diphenylene or triisopropylphenylene; R is alkyl having up to four carbon atoms, allyl, methoxymethyl, phenyl, pentachlorophenyl or naphthyl; R is alkyl having up to four carbon atoms and R and R are each alkyl having up to four carbon atoms, amyl, phenyl, toluyl or naphthyl.

4. The solution of claim 1 wherein the molar ratio of (a):(b):(c) is from about 2:1:2 to about 625:2.

5. The solution of claim 1 wherein the molar ratio of (a):(b):(c) is from about 1:2:2 to about 5:6:2.

said 

2. The solution of claim 1 wherein said copolymerizable monomer is styrene.
 3. The solution of claim 1 wherein Ar is phenyl, monochlorophenyl, pentachlorophenyl, toluyl, diphenyl or naphthyl; R is alkylene having up to six carbon atoms, phenylene, toluylene, diphenylene or triisopropylphenylene; R1 is alkyl having up to four carbon atoms, allyl, methoxymethyl, phenyl, pentachlorophenyl or naphthyl; R4 is alkyl having up to four carbon atoms and R5 and R6 are each alkyl having up to four carbon atoms, amyl, phenyl, toluyl or naphthyl.
 4. The solution of claim 1 wherein the molar ratio of (a):(b): (c) is from about 2:1:2 to about 6:5:2.
 5. The solution of claim 1 wherein the molar ratio of (a):(b): (c) is from about 1:2:2 to about 5:6:2. 